Tirath Rama,
Neeraj Vermaa,
Jagjeet Kaura,
Abhishek Kumar Misraa,
Vikas Dubey*b,
Neha Dubeya,
Marta Michalska-Domańska*c,
Janita Sajid and
Ram Sagar Yadave
aDepartment of Physics, Government Vishwanath Yadav Tamaskar Post Graduate Autonomous College, Durg, C.G., India
bDepartment of Physics, North Eastern Hill University (NEHU), Shillong, Meghalaya 493022, India. E-mail: jsvikasdubey@gmail.com
cInstitute of Optoelectronics, Military University of Technology, Kaliskiego 2, 00-908 Warsaw, Mazovia, Poland
dDepartment of Sciences and Humanities, School of Engineering and Technology CHRIST (Deemed to be University), Bangalore, India
eDepartment of Statistics, Institute of Science, Banaras Hindu University, Varanasi, 221005, India
First published on 4th September 2023
The solid-state reaction method was utilised to create a down-conversion phosphor in an air environment in CaY2O4:Eu3+ nanocrystalline material. The calcination temperature was set at 1000 °C, and the sintering temperature was set at 1300 °C. Following annealing, confirmation of the crystallinity quality of the phosphor was accomplished by the use of X-ray diffraction analysis. The particle size was predicted to be 43.113 nm using Scherrer's formula. To produce down-conversion luminescence spectra, an excitation wavelength of 247 nm was applied with a fluorescence spectrophotometer. The PL got increasingly intense as the concentration of the dopant increased. The maximum intensity was measured at 2.0 mol% of Eu3+ ion, which gradually decreased as the concentration increased because of concentration quenching. To analyse spectrophotometric peak determinations, the approach developed by the Commission Internationale de l'Éclairage (CIE) was used. Thermoluminescence (TL) glow curve analysis of the CaY2O4:Eu3+-doped phosphor manufactured here revealed a wide TL centred at 225 °C, which comprised of so many peaks that may be extracted by the computerised glow curve deconvolution (CGCD) approach using glow-fit software. The associated kinetic parameters were then determined. The prepared phosphor may be useful for application in various display devices upon excitation by 247 nm; the prominent 613 nm peak of the Eu3+ ion (5D0 → 7F2) electric dipole transition features a red component. CaY2O4:Eu3+ phosphors show promise as materials for potential use in phosphor-converted white LEDs in the field of solid-state lighting technology. The linear connection that the TL glow curve has with UV dose provides evidence for its possible use in dosimetry.
P. Tadge et al. studied the downshifting, frequency up-conversion, and intrinsic optical bi-stability in CaY2O4:Ho3+/Yb3+ and CaSc2O4:Ho3+/Yb3+ phosphors that were synthesised by a complex-based precursor solution method. The X-ray powder diffraction confirmed the formation of highly crystalline phosphors with a pure orthorhombic phase. Fourier transform infrared studies showed vibrational bands and diffuse reflectance spectra. The Ho3+/Yb3+ co-doped CaSc2O4 and CaY2O4 phosphors display intense green downshifting emission upon 454 nm excitations. Their decay curves indicated a non-exponential nature, and the energy transfer microscopic parameters were calculated.18
Jeon et al. discussed up-conversion to be an anti-stokes process that converted near-infrared light into visible light. CaY2O4 is a promising host material due to its high chemical and thermal stability, low-phonon energy, and environment friendliness. Er3+ and Yb3+-doped nano-crystalline phosphors were prepared by a sol–gel process that was characterised by X-ray diffraction and scanning electron microscopy. Photoluminescence properties of the powders were measured by exciting them with a 980 nm diode laser at room temperature. Green and red up-conversion emissions were observed at 520–540 nm, 540–570 nm, and 640–680 nm.19
Hwang et al. studied the nanocrystalline CaY2O4:Er3+ up-conversion phosphor prepared by the sol–gel process. A homogeneous precursor sol was heated on a hot plate; the coagulated gel was pre-fired at 300 °C for 4 h under an Ar atmosphere, followed by final annealing at 1200 °C for 4 h. The crystallinity of the powders after annealing was confirmed using an X-ray diffraction analysis. The shape and particle size of the powders were observed by field emission-scanning electron microscope and transmission electron microscope. The particle size of CaY2O4 powder that had been doped (3 mol%) was homogeneous and varied from 100 to 200 nm, according to micrographic pictures. When Er3+ is injected at a 3 mol% doping concentration, up-conversion efficiency is at its maximum. Additionally, the excellent colour purity of the phosphor exhibits colour tunability.20
Because of its remarkable thermoluminescence (TL) capabilities, CaY2O4:Eu3+ phosphor has been widely recognised as a very effective material for radiation dosimetry. This phosphor exhibits remarkable TL intensity and chemical stability, minimal fading rate, and resistance to environmental variations. Many environmental16,17 and personnel monitoring18,19 programs use it. Since the overall energy contained in the phosphor is emitted in a single measurement during the TL readout, any TL reader malfunctioning during measurements would result in a spurious TL readout. TL-grade CaY2O4:Eu3+ was found to present photo-stimulated luminescence that varies with the dosage. This discovery holds significant potential for radiation dosimetry as it enables multiple outputs on a phosphor sample that has been exposed to radiation, without significant loss of stored energy.20 Consequently, this method offers an advantage over the commonly employed TL method, which lacks this capability.
If we can enhance the declining property, a phosphor that is primarily composed of CaY2O4 has the potential to resemble an optimal TL dosimeter material, aside from the issue of tissue equivalence.21,22
The phosphors mentioned in this paper are CaY2O4:Eu3+; these newly synthesised phosphors exhibit minimum fading, while retaining nearly all of the other beneficial properties of CaSO4:Mn. Dosimeters are constructed with these phosphors, and their properties are studied from the perspective of radiation dosimetry.23
The current research focuses on the creation and analysis of a phosphor material that incorporates Eu3+ ions. This synthesised phosphor demonstrates the potential for a wide range of applications, including displays and dosimetry. As the synthesised phosphor features a crystalline quality as per XRD analysis, to study the morphology of the prepared phosphor, SEM analysis was performed; functional group and modes of vibration were studied by FTIR; spectroscopic analysis was performed using PL emission and excitation spectra, while colour optimisation was done through CIE coordinate and trap parameter analysis was conducted using a TL glow curve analysis via the CGCD technique.
CaCO3 + Y2O3 → CaY2O4 + CO2 |
Y2O3 + CaCO3 + Eu2O3 → CaY2O4:Eu3 |
To determine the crystalline quality of the phosphor and its particle size, X-ray diffraction studies were performed (Advanced Bruker D8 from Germany). We used a CuKα source in an X-ray diffractometer to collect data with X-ray powder diffraction analysis. The X-rays, having a wavelength of 0.154 nm, were produced within a hermetically sealed tube. To detect the X-rays, a high-speed silicon strip technology-based detector known as the Bruker Lynx Eye detector was employed (Bruker made in Germany). To ascertain the molecular structure, FTIR analysis was carried out. A Shimadzu RF-5301 PC spectrofluorophotometer was used to obtain both the emission and excitation spectra of the PL. At room temperature, glow curves of thermally stimulated luminescence (TSL) were recorded using a TLD reader I1009 that was supplied by Nucleonix Sys. Pvt. Ltd in Hyderabad. In the course of the TL test, the phosphor was subjected to UV light coming from a source emitting 254 nm of UV.9,24,25,35
Scherrer's formula for the calculation of crystallite size is as follows:
In this context, the size of the crystallites is represented in this situation by the variable D. The FWHM is represented by the symbol β. The wavelength of the X-ray source is indicated by the symbol λ, while the diffraction angle is shown by the symbol θ. According to Table 1,
D = (0.9 × 0.15409)/(RADIANS(0.19309) × COS(RADIANS(27.07759)/2)) |
hkl | Peak position (2θ) | FWHM | Crystallite size D (nm) | Average size D (nm) |
---|---|---|---|---|
111 | 27.07759 | 0.19309 | 42.32714752 | 43.113 |
200 | 31.7155 | 0.21663 | 38.1304235 | |
220 | 46.44312 | 0.19783 | 43.70569803 | |
222 | 55.52602 | 0.19785 | 45.38561618 | |
420 | 76.4881 | 0.21986 | 46.01642362 |
The average crystallite size is 43.113 nm.
The excitation spectra of CaY2O4:Eu3+ phosphor were recorded by monitoring the Eu3+ 5D0 → 7F2 transition at 613 nm. A large peak at 247 nm was seen in the excitation spectra, followed by another broad peak at 344 nm due to the 7F0 → 5D4 transition. The maximum absorption intensity was observed at these two wavelengths. The excitation spectra (shown in Fig. 6a) included a prominent wide band with a peak at 247 nm, which is attributed to the charge transfer band (CTB) between Eu3+ and O2− neighbouring ions. Lines owing to the f–f transitions in the Eu3+ 4f6 arrangement were also seen at longer wavelengths.29,30
The emission spectrum of the phosphor was measured by exciting them with 247 nm, and the results are depicted in Fig. 6b. The spectrum comprises 5D0–7FJ (J = 1, 2, and 3) emission lines of Eu3+. When Eu3+ occupies a crystallographic position devoid of inversion symmetry, the red-forced electric-dipole transition 5D0 → 7F2 often dominates the emission spectrum. On the other hand, if the Eu3+ site has an inversion centre, the 5D0 → 7F1 orange emission dominates.31 The transitions from excited 5D0 to the 7FJ (J = 0–3) levels of Eu3+ ions produce distinctive emission lines within the 535–650 nm range. The placement of the Eu3+ ion in the CaY2O4 lattice, in combination with the selection criteria, determines the kind of transition from the emission levels to the terminating levels.32,33,36–39
The prominent peak at 613 nm is due to the electric dipole (ED) transition between the 5D0 and 7F2 levels, whereas the faint emission at 593 nm is due to a forced magnetic dipole (MD) transition process. The emission spectrum of the CaY2O4:Eu3+ sample displays peaks ranging from 535–650 nm, which arise from the 5D0 → 7FJ (J = 1, 2) transitions of Eu3+ ions upon excitation at 247 nm. The 535 nm, 613 nm, and 631 nm peaks are attributed to the ED transition of 5D0 → 7F1 and (5D0 → 7F2), respectively, with the 613 nm peak having twice the intensity of the 593 nm peak. The ratio of the 593 nm peak intensity to the 613 and 631 nm peaks is half, which differs from previous research findings. This suggests that the Eu3+ ions are located at a site with low symmetry in the CaY2O4 host, as the MD transition has a lower intensity than the ED transition. However, at a concentration of 2.0 mol% of Eu3+, concentration quenching occurs as a consequence of energy transfer between Eu3+ ions, and the peak locations of the emission spectra alter. Therefore, the CaY2O4:Eu3+ (2.0 mol%) phosphor could be a promising candidate for use in compact fluorescent lamps (CFLs) with excitation at 247 nm.
Fig. 7 shows the energy-level diagram of the Eu3+ ion in terms of the ED transition peak at 613 nm (5D0 → 7F2) and the dominant MD transition peak at 593 nm (5D0 → 7F1).
Fig. 8 presents a distinct and wide TL glow curve with its peak centred at 225 °C. The intensity of the TL glow curve demonstrates an upward trend as the concentration of doping ions increases, reaching its highest point at 2 mol%. Concentration quenching caused a loss of intensity after going over the highest point. This particular TL glow curve was obtained after a 20 minute exposure to UV radiation and is considered suitable for dosimetry applications. The concentration versus intensity plot is shown in Fig. 9 for better understanding.
As well-resolved broad TL glow curve was monitored in the dose versus intensity plot with various UV doses and 5–25 min UV exposure time (Fig. 10). Here, the intensity of the glow curve was measured at a fixed (optimised) concentration of 2.0 mol% of doping ion; it increased with increasing UV radiation exposure (Fig. 11). The well-resolved peak showed good linearity with the dose which showed the prepared phosphor could be useful for dosimetric applications.
CGCD-fitted TL glow curves of CaY2O4:Eu3+ phosphor (Fig. 12) that were exposed to UV radiation for 20 minutes are shown in Fig. 10. Table 2 displays a variety of trapping characteristics, including activation energy, order of kinetics, and frequency factors. After being exposed to UV light, the prepared sample's trap depth decreased from 0.5 to 1.0412 eV as shown by the fit, suggesting the creation of shallower traps. Irradiation by the UV rays from a lower energy source would have resulted in the formation of shallow trap levels, where electrons need less energy to tunnel through the barrier and recombine; hence, activation energy is lower for UV-irradiated samples. Fig. 12 shows the CGCD pattern of the optimised concentration (2 mol%) of the dopant with 25 min of UV exposure time; this pattern was composed of five distinct peaks, and Table 2 shows the calculated trap parameters of the CGCD pattern (a value of merit is 1.09%). It shows that the first order of kinetic and activation energies vary from 0.5 to 1.0412 eV, and the frequency factor values are very high, i.e., 4.52 × 108 s−1 for the second fitted peak.
Fig. 12 CGCD of UV-induced CaY2O4:Eu3+-doped phosphor for optimised UV dose and 2.0 mol% concentration. |
T1 (K) | Tm (K) | T2 (K) | τ | δ | ω | μ = δ/ω | Activation energy (eV) | Frequency factor (s−1) |
---|---|---|---|---|---|---|---|---|
311 | 338 | 359 | 27 | 21 | 48 | 0.4375 | 0.5 | 2.18 × 108 |
350 | 382 | 406 | 32 | 24 | 56 | 0.4285714 | 0.5001 | 2.14 × 108 |
406 | 452 | 485 | 46 | 33 | 79 | 0.4177215 | 0.5002 | 2.08 × 108 |
452 | 503 | 543 | 51 | 40 | 91 | 0.4395604 | 0.5275 | 2.31 × 108 |
505 | 564 | 608 | 59 | 44 | 103 | 0.4271845 | 0.5902 | 2.52 × 108 |
597 | 640 | 673 | 43 | 33 | 76 | 0.4342105 | 1.0412 | 4.52 × 108 |
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